Pb(Hf,Ti)O3 based high performance polycrystalline piezoelectric materials

ABSTRACT

A ternary polycrystalline material based on lead hafnate (PbHfO 3 ) and having improved dielectric, piezoelectric, and/or thermal stability properties. The Pb(Hf,Ti)O 3  based material can exhibit enhanced electromechanical coupling factors when compared to PZT based ceramics and can be used as high performance actuators, piezoelectric sensors and/or ultrasonic transducers. The ternary polycrystalline material can have a perovskite crystal structure with an ABO 3  formula and can be characterized by a substitution of heterovalent acceptor and donor ions at A or B (Zr/Hf) sites.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority of U.S. Provisional Application 61/581,365, filed Dec. 29, 2011, the contents of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention is related to a piezoelectric material, and in particular, a high performance polycrystalline piezoelectric material based on lead hafnate.

BACKGROUND OF THE INVENTION

For the past 60 years, perovskite Pb(Zr_(x)Ti_(1-x))O₃ (PZT) piezoelectric ceramics have dominated the commercial market of piezoelectric sensors, actuators and medical ultrasonic transducers due to their high dielectric, piezoelectric and electromechanical coupling factor properties. In addition, the properties of PZT piezoelectric ceramics can be further modified with different additives and/or dopants. In particular, PZT piezoelectric ceramics with compositions in the vicinity of a morphotropic phase boundary (MPB) that separates a rhombohedral phase from a tetragonal ferroelectric phase can exhibit anomalously high dielectric and piezoelectric properties. The high properties are the result of enhanced polarizability from the coupling between two equivalent energy states, i.e. between a tetragonal phase and a rhombohedral phase, which allows optimum domain reorientation during poling.

Numerous PZT formulations/compositions have been engineered for specific characteristics that enhance their use in many applications. For example, Tables I and II list the properties of commercially available soft PZT ceramics, and FIGS. 1 and 2 provide plots of dielectric permittivity and piezoelectric coefficient d₃₃ versus Curie temperature (T_(C)) for such materials. As shown by the data, polycrystalline materials with higher Curie temperatures generally possess lower dielectric and piezoelectric properties.

TABLE I Piezoelectric, dielectric and ferroelectric properties of commercial PZT5A type ceramics. P_(r) d₃₃ k_(p) tanδ T_(C) (μC/ E_(C) PZT5H (pC/N) (%) ε_(r) (%) (° C.) cm²) (kV/cm) TRS200HD¹ 400 0.66 2000 1.8 340 / / 3195STD² 350 0.63 1800 1.8 350 39 14.9 3295HD² 390 0.65 1900 1.8 350 39 12.0 PIC255³ 400 0.62 1750 2.0 350 / / PIC155³ 360 0.62 1450 2.0 345 / / PKI502⁴ 425 0.60 2000 1.5 350 / / PZ23⁵ 328 0.52 1500 1.3 350 / / PZ27⁵ 425 0.59 1800 1.7 350 / / PZT5A1⁶ 410 0.62 1875 2.0 370 / / PZT5A3⁶ 374 0.60 1700 2.0 365 / / ¹TRS Technologies; ²CTS; ³PIceramic; ⁴Piezo-kinetics; ⁵Ferroperm; ⁶Morgan.

TABLE II Piezoelectric, dielectric and ferroelectric properties of commercial PZT5H type ceramics. P_(r) d₃₃ k_(p) tanδ T_(C) (μC/ E_(C) PZT5H (pC/N) (%) ε_(r) (%) (° C.) cm²) (kV/cm) TRS610HD¹ 690 0.70 3900 1.8 210 / / CTS3203STD² 550 0.69 3250 2.0 235 37 10.6 CTS3203HD² 650 0.70 3800 2.0 225 39  8.0 PIC151³ 500 0.62 2400 2.0 250 / / PIC153³ 600 0.62 4200 3.0 185 / / PKI532⁴ 490 0.63 2700 2.0 220 / / PKI552⁴ 600 0.67 3400 2.2 200 / / PZ21⁵ 640 0.60 3980 1.6 218 / / PZ29⁵ 570 0.64 2870 1.6 235 / / PZT5H1⁶ 620 0.60 3400 1.8 200 / / PZT5H2⁶ 590 0.65 3400 2.5 195 / / ¹TRS Technologies; ²CTS; ³PIceramic; ⁴Piezo-kinetics; ⁵Ferroperm; ⁶Morgan.

It is appreciated that innovations in electronic devices have been the driving force for new developments in piezoelectric ceramics. In fact, and in order to meet the newly developed electromechanical devices, materials with Curie temperatures equivalent to heretofore developed materials but with higher dielectric and piezoelectric properties, and/or materials with similar dielectric and piezoelectric properties but higher Curie temperatures, are desired.

In addition to the above, the electromechanical coupling factor—the square of which is closely related to output power density—is known to be an important material parameter in ultrasonic transducer applications and the dielectric variation for prior art PZT based materials is relatively broad and on the order of 2000-8000 ppm/° C. Therefore, a new polycrystalline piezoelectric material with increased electromechanical coupling factor and reduced dielectric variation would also be desirable.

SUMMARY OF THE INVENTION

Ternary polycrystalline materials based on lead hafnate (PbHfO₃) and having improved dielectric, piezoelectric, and/or thermal stability properties are provided. In addition, the PbHfO₃ based materials can exhibit enhanced electromechanical coupling factors when compared to PZT based ceramics. The inventive materials can be used as high performance actuators, piezoelectric sensors and/or ultrasonic transducers.

In particular, the ternary polycrystalline materials provide piezoelectric ceramic materials based on lead hafnium titanate, e.g. PbHfO₃—PbTiO₃ (PHI), that have a perovskite crystal structure with an ABO₃ formula and are characterized by a substitution of heterovalent acceptor and donor ions at Zr/Hf sites. In addition, Pb(M_(I) ³⁺ _(1/3), M_(II) ⁵⁺ _(2/3))O₃—PHT ternary systems are provided that have: (1) equivalent Curie temperatures as prior art PZT based ceramics but exhibit higher dielectric and piezoelectric properties when compared thereto; and/or (2) comparable dielectric and piezoelectric properties as prior art PZT based ceramics but exhibit higher Curie temperatures when compared thereto.

In some instances, the ternary polycrystalline materials have a formula of Pb_(1-x)M_(x) [{M_(I) ²⁺}_(1/3){M_(II) ⁵⁺}_(2/3)]_(1-y-z)Hf_(z)Ti_(y)O₃, where M is Ba²⁺, Ca²⁺, Sr²⁺, La³⁺ and the like; M_(I) is Mg²⁺, Zn²⁺, Ni²⁺ and the like; M_(II) is Nb⁵⁺, Ta⁵⁺, Sb⁵⁺ and the like; x is greater than or equal to 0.0 and less than 0.2; y is greater than 0.3 and less than 0.7, in some instances greater than 0.2 and less than 0.8; and z is greater than 0.3 and less than 0.7, in some instances greater than 0.2 and less than 0.8. In other instances, the ternary piezoelectric polycrystalline material has a formula of Pb_(1-x)M_(x) [{M_(I) ³⁺}_(1/2){M_(II) ⁵⁺}_(1/2)]_(1-y-z)Hf_(z)Ti_(y)O₃, where M_(I) ³⁺ is Yb³⁺, Sc³⁺, In³⁺ and Hf⁴⁺ or Ti⁴⁺ ions are at least partially replaced with donor dopants or acceptor dopants. The donor dopants can be Nb⁵⁺, Ta⁵⁺, W⁵⁺ and the like and the acceptor dopants can be Fe^(2+, 3+), Co^(2+, 3+), Mn^(2+,3+) and the like. In addition, M is Ba²⁺, Ca²⁺, Sr²⁺, La³⁺ and the like; M_(II) is Nb⁵⁺, Ta⁵⁺, Sb⁵⁺ and the like; x is greater than or equal to 0.0 and less than 0.2; y is greater than 0.3 and less than 0.7, in some instances greater than 0.2 and less than 0.8; and z is greater than 0.3 and less than 0.7, in some instances greater than 0.2 and less than 0.8.

The inventive material can have a Curie temperature in the range of 180° C. to 280° C. and a piezoelectric coefficient d₃₃ greater than 600 pC/N, a Curie temperature of greater than 300° C. and a piezoelectric coefficient d₃₃ greater than 500 pC/N, a Curie temperature in the range of 260-300° C. and a piezoelectric coefficient d₃₃ in the range of 450-680 pC/N, and/or a Curie temperature greater than 120° C. and a piezoelectric coefficient d₃₃ greater than 800 pC/N. In addition, the material can have electromechanical coupling k₃₃ within a range of about 0.707-0.775.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical plot illustrating dielectric permittivity as a function of Curie temperature for PZT piezoelectric ceramics;

FIG. 2 is a graphical plot illustrating piezoelectric coefficient d₃₃ as a function of Curie temperature for PZT piezoelectric ceramics;

FIG. 3 is a graphical plot illustrating Curie temperature versus amount of PMN for pellets having a composition formula of (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN with various levels of lead titanate (PT);

FIG. 4 is an isothermal map of Currie temperature (T_(C)) for (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN;

FIG. 5 a is a graphical plot illustrating piezoelectric coefficient d₃₃ as a function of PMN content;

FIG. 5 b is a graphical plot illustrating planar electrochemical coupling k_(p) as a function of PMN content;

FIG. 6 is a graphical plot with data from the inventive materials shown in Tables III-V superimposed on data shown in FIG. 1;

FIG. 7 is a graphical plot with data from the inventive materials shown in Tables III-V superimposed on data shown in FIG. 2; and

FIG. 8 is a graphical plot of electromechanical coupling factor squared (k₃₃ ²) as a function of Currie temperature for prior art PZT based ceramics and the inventive PHT based ceramics disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

Inventive lead hafnium titanate-lead magnesium niobate (PHT-PMN) ternary ceramics with compositions of (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPb(Mg_(1/3)Nb_(2/3))O₃ ((1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN, x=0˜0.5, y=0.515˜0.7) are provided. For example and for illustrative purposes only, an example of how typical PHT-PMN ternary ceramics according to one or more embodiments of the present invention were produced and associated properties are described below.

The inventive materials were prepared using a two-step precursor method. Raw materials of MgCO₃ (99.9%, Alfa Aesar, Ward Hill, Mass.), Nb₂O₅ (99.9%, Alfa Aesar), HfO₂ (99.9%, Alfa Aesar) and TiO₂ (99.9%, Ishihara, San Francisco, Calif.) were used to synthesize columbite precursors of MgNb₂O₆ and Hf_(0.45)Ti_(0.55)O₂ at 1000° C. and 1200° C., respectively. Thereafter, Pb₃O₄ (99%, Alfa Aesar) and the MgNb₂O₆ and Hf_(0.45)Ti_(0.55)O₂ percursor powders were batched stoichiometrically by wet-milling in alcohol for 24 hours (h). Dried mixed powders of the Pb₃O₄, MgNb₂O₆ and Hf_(0.45)Ti_(0.55)O₂ were then calcined at 800° C. for 4 h to produce synthesized powders which were subsequently vibratory milled in alcohol for 12 h. The synthesized powders were then granulated and pressed into pellets having a 12 mm diameter, followed by a binder burnout at 550° C. and sintering in a sealed crucible at 1250° C. In order to minimize PbO evaporation during sintering, PbZrO₃ was used as a lead (Pb) source in the sealed crucible.

Sintered pellets were tested for temperature dependence of dielectric permittivity with FIG. 3 illustrating Curie temperature (T_(C)) versus amount of PMN for pellets having a composition formula of (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN with various levels of lead titanate (PT). As shown in the figure, increasing the PMN content resulted in a monotonic T_(C) decrease from 360-285° C., 340-270° C., 320-255° C., 328-243° C. and 234-186° C. for the different PT levels corresponding to y=0.515, 0.534, 0.555, 0.574 and 0.7, respectively. Furthermore, with increasing PMN content, the ternary solid solution exhibited more relaxor-like characteristics, showing broadened dielectric peaks and dispersive dielectric behavior with respect to frequency.

Based on the above results, an isothermal map of Currie temperature (T_(C)) for (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN was developed and is shown in FIG. 4. It is appreciated that along the MPB line from the PH-PT side towards the PMN-PT side, T_(C) gradually decreases from 325° C. to 200° C. It is appreciated that this decrease in T_(C) could be due to an increase of PMN content in the sintered pellets that were tested.

The dielectric, piezoelectric and electromechanical properties of all studied (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPMN compositions are summarized in Table III. In addition, the piezoelectric coefficient d₃₃ and planar electromechanical coupling k_(p) as a function of PMN are shown in FIGS. 5 a and 5 b, respectively. As shown in the figures, optimum piezoelectric and electromechanical properties where exhibited for specific compositions and it is appreciated that the optimum properties could be due to enhanced polarizability arising from coupling between tetragonal and rhombohedral phases. In addition, the optimum piezoelectric and electromechanical properties were achieved for the composition 0.8Pb(Hf_(0.445)Ti_(0.555))O₃-0.2Pb(Mg_(1/3)Nb_(2/3))O₃, with dielectric permittivity ∈_(r), piezoelectric coefficient d₃₃, planar electromechanical coupling k_(p) and T_(C) being on the order of 2870, 680 pC/N, 70% and 276° C., respectively.

TABLE III Piezoelectric, dielectric and ferroelectric properties of (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPMN ternary ceramics. d₃₃ k_(p) tanδ T_(C) P_(r) E_(C) (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPMN (pC/N) (%) ε_(r) (%) (° C.) (μC/cm²) (kV/cm) y = 0.515 x = 0 210 37 1220 1.1 360 13 13.2 x = 0.05 280 41 1560 1.6 333 25 11.9 x = 0.1 430 62 1100 2.1 306 37 8.8 x = 0.15 330 58 870 2.4 285 39 8.3 y = 0.534 x = 0.05 190 32 1350 1.4 340 18 14.4 x = 0.1 450 58 2030 1.4 312 32 15 x = 0.15 600 69 2330 1.9 291 40 9.4 x = 0.2 320 59 960 2.2 271 36 8.1 y = 0.555 x = 0.1 360 37 1300 1.4 321 23 17.3 x = 0.15 430 57 2120 1.4 296 32 15.2 x = 0.18 580 65 2770 1.5 286 37 11.3 x = 0.19 640 68 2810 1.5 278 40 10.3 x = 0.2 680 70 2870 1.7 276 40 9.9 x = 0.21 590 69 2040 1.6 271 42 9.3 x = 0.22 490 68 1630 1.8 268 40 8.4 x = 0.25 340 60 1020 2.2 255 38 7.9 y = 0.574 x = 0.1 160 32 1050 1.3 328 22 19.9 x = 0.15 300 49 1550 1.2 304 31 19.4 x = 0.2 440 58 2360 1.4 283 34 13.3 x = 0.24 670 69 2960 1.4 263 41 9.5 x = 0.25 640 65 2470 1.6 262 38 9.3 x = 0.26 580 65 1900 1.6 / 41 8.6 x = 0.3 230 48 1120 2.2 243 28 7.1 y = 0.7 x = 0.4 330 46 2360 0.8 234 26 10.7 x = 0.45 390 54 2050 1.1 213 30 7.3 x = 0.47 540 66 2090 1.3 201 37 7 x = 0.5 400 60 1420 1.8 186 36 5.9

The main properties of other systems, such as (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPb(Ni_(1/3)Nb_(2/3))O₃ (PHT-PNN), (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPb(Sc_(0.5)Nb_(0.5))O₃ (PHT-PSN) and (1-x)Pb(Hf_(1-y)Ti_(y))O₃-xPb(Zn_(1/3)Nb_(2/3))O₃ (PHT-PZN), are given in Tables IV and V below, respectively.

TABLE IV Piezoelectric, dielectric and ferroelectric properties of (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPNN ternary ceramics. d₃₃ k_(p) loss T_(C) Pr E_(c) Samples (pC/N) (%) K (%) (° C.) (μC/cm²) (kV/cm) y = 0.55 x = 5 160 35 1050 1.0 337 10 12 10 280 43 1400 1.2 310 16 12 15 340 49 1830 1.8 280 24 10.7 18 495 61 2140 1.7 260 29 8 19 470 61 1970 1.6 256 28 7.5 20 435 61 1870 1.8 250 31 7.5 22 380 60 1250 1.7 238 34 7.3 25 350 60 1180 1.8 222 36 7.2 y = 0.57 x = 10 170 1030 1.1 — 15 250 39 1280 1.4 292 19 13.7 19 350 47 1950 1.5 266 21 10.2 20 360 49 2000 1.5 257 23 10.2 21 420 57 2100 1.55 252 27 9.8 22 480 57 2600 1.77 246 28 9 23 550 65 2650 1.8 240 32 8.8 25 595 66 2200 1.66 229 34 7.6 20 320 50 2000 1.2 260 24 11.5 22 410 54 2390 1.3 250 28 10.1 23 460 57 2600 1.38 244 29 9.8 24 530 61 2850 1.4 235 31 9.4 25 610 65 3000 1.5 234 33 8.6 26 650 68 2950 1.6 227 35 8.5 26.5 630 67 2430 1.5 225 35 8.4 27 660 68 2200 1.35 221 37 7.5 28 530 65 2270 1.5 215 36 7 30 460 64 2000 1.7 204 36 6.4 y = 0.60 x = 25 570 63 3200 1.46 225 29 9.5 28 650 67 3450 1.5 220 31 9 29 700 69 3610 1.7 214 32 8.3 30 765 70 3800 2.0 210 32 7.4 30.5 795 71 3600 2.0 206 33 7.2 31 760 71 3250 2.0 203 34 7.2 31.5 730 71 2940 1.8 — 35 6.9 32 690 70 2880 1.75 199 34 6.6 33 640 68 2350 1.75 191 34 6.2 y = 0.70 x = 30 300 47 1900 1.4 208 25 12.5 40 445 51 2700 1.3 184 26 9 42 540 55 3600 1.65 168 26 6 44 650 58 4500 1.85 155 26 6.7 45 725 60 4950 1.98 151 26 6.5 46 800 61 5500 1.8 145 27 5.6 47 865 63 5830 2.3 138 27 5.1 48 940 65 5240 2.4 120 27 3.8 49 970 65 6000 2.5 — 27 4.2 50 930 65 5930 2.38 — 27 4.3

TABLE V Piezoelectric, dielectric and ferroelectric properties of (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPSN and (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPZN ternary ceramics. Pr Materials d₃₃ k_(p) loss T_(C) (μC/ E_(c) y x (pC/N) (%) K (%) (° C.) cm²) (kV/cm) (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPSN 0.60 0.20 550 65 2420 1.5 325 38 10.6 0.575 0.175 600 71 2220 1.6 325 43 9.4 0.55 0.12 590 70 2250 1.6 334 43 9.5 0.55 0.125 560 67 1950 1.7 330 41 9.2 (1 − x)Pb(Hf_(1−y)Ti_(y))O₃-xPZN 0.519 0.20 500 70 1650 2.0 292 42 9.1 0.525 0.20 530 69 2060 2.0 295 41 10.3 0.525 0.25 510 68 1900 2.0 280 41 9.9 0.539 0.225 570 68 2300 2.0 292 38 11.6

In order to provide a clearer view of the enhanced properties exhibited by the inventive materials, FIGS. 6 and 7 are plots of data from Tables III-V above compared to the data shown in FIGS. 1 and 2. The data from Tables III-V are labeled as PHT based ceramics, versus the data from FIGS. 1 and 2 which are labeled as PZT based ceramics. As shown in the figures, a comparable dielectric permittivity with significant higher d₃₃ coefficient is exhibited by the inventive materials compared to heretofore polycrystalline piezoelectric materials. In addition, FIG. 8 provides a plot of the electromechanical coupling factor squared (k₃₃ ²) as a function of T_(C) for prior art PZT based ceramics and the inventive PHT based ceramics. Again, a significant improvement in output power density is expected by the ternary PHT polycrystalline piezoelectric materials disclosed herein.

The invention is not restricted to the illustrative examples and embodiments described above. The examples are not intended as limitations on the scope of the invention. Methods, apparatus, compositions, and the like described herein are exemplary and not intended as limitations on the scope of the invention. Changes therein and others will occur to those skilled in the art and, as such, the specification and the appendices should be interpreted broadly. 

We claim:
 1. A ternary piezoelectric polycrystalline material comprising: a lead hafnium titanate containing ceramic having a formula of Pb_(1-x)M_(x) [{M_(I) ²⁺}_(1/3){M_(II) ⁵⁺}_(2/3)]_(1-y-z)Hf_(z)Ti_(y)O₃, where: M is at least one of Ba²⁺, Ca²⁺, Sr²⁺ and La³⁺; M_(I) ²⁺ is at least one of Mg²⁺, Ni²⁺ and Zn²⁺; M_(II) ⁵⁺ is at least one of Nb⁵⁺, Sb⁵⁺ and Ta⁵⁺; x is greater than 0.0 and less than 0.2; y is greater than 0.2 and less than 0.8; and z is greater than 0.2 and less than 0.8.
 2. The composition of claim 1, wherein said lead hafnium titanate containing ceramic has a Curie temperature in the range of 180° C. to 280° C. and a piezoelectric coefficient d₃₃ greater than 600 pC/N.
 3. The composition of claim 1, wherein said lead hafnium titanate containing ceramic has a Curie temperature of greater than 300° C., a piezoelectric coefficient d₃₃ greater than 500 pC/N and electromechanical coupling k₃₃ within a range of 0.707 to 0.775.
 4. The composition of claim 1, wherein said lead hafnium titanate containing ceramic has a Curie temperature in the range of 260-300° C. and a piezoelectric coefficient d₃₃ in the range of 450-680 pC/N.
 5. The composition of claim 1, wherein said lead hafnium titanate containing ceramic has a Curie temperature greater than 120° C. and a piezoelectric coefficient d₃₃ greater than 800 pC/N.
 6. A ternary piezoelectric polycrystalline material comprising: a lead hafnium titanate containing ceramic having a formula of Pb_(1-x)M_(x) [{M_(I) ³⁺}_(1/3){M_(II) ⁵⁺}_(2/3)]_(1-y-z)Hf_(z)Ti_(y)O₃ where: M is at least one of Ba²⁺, Ca²⁺, Sr²⁺ and La³⁺; M_(I) ³⁺ is at least one of Yb³⁺, Sc³⁺, In³⁺, Fe³⁺ and Co³⁺; M_(II) ⁵⁺ is at least one of Nb⁵⁺, Sb⁵⁺ and Ta⁵⁺; X is greater than 0.0 and less than 0.2; y is greater than 0.2 and less than 0.8; z is greater than 0.2 and less than 0.8; and Hf⁴⁺ or Ti⁴⁺ ions are at least partially replaced with donor dopants or acceptor dopants; said donor dopants being at least one of Nb⁵⁺, Ta⁵⁺ and W⁵⁺; and said acceptor dopants being at least one of Fe²⁺, Co^(2α,3+), Co^(2+,3+), Mn^(2+,3+), Cu^(+,2+).
 7. The composition of claim 6, wherein said lead hafnium titanate containing ceramic has a Curie temperature in the range of 180° C. to 280° C. and a piezoelectric coefficient d₃₃ greater than 600 pC/N.
 8. The composition of claim 6, wherein said lead hafnium titanate containing ceramic has a Curie temperature of greater than 300° C., a piezoelectric coefficient d₃₃ greater than 500 pC/N and electromechanical coupling k₃₃ within a range of 0.707-0.775.
 9. The composition of claim 6, wherein said lead hafnium titanate containing ceramic has a Curie temperature in the range of 260-300° C. and a piezoelectric coefficient d₃₃ in the range of 450-680 pC/N.
 10. The composition of claim 6, wherein said lead hafnium titanate containing ceramic has a Curie temperature greater than 120° C. and a piezoelectric coefficient d₃₃ greater than 800 pC/N. 